Aliphatic polyether substituted ferrocene



3,322,804 Patented May 30, 1967 United States Patent Oflice 3,322,804 HrALIPHATIC POLYETHER SUBSTITUTED FERROCENE Roy L. Pruett, Charleston, W.Va., assignor to Union Carbide Corporation, a corporation of New York 5No Drawing. Filed June 11, 1963, Ser. No. 286,947

6 Claims. (Cl. 260-439) C This invention relates to a novel-aliphaticpolyether substituted ferrocene. 10 Ferrocene is an art term for thecompound bis(cyclo- H H5 pentadienyl)iron. This compound has evokedconsiderable interest resulting in the manufacture of a variety ofderivatives. This invention relates to a derivative of ferrocene l1 H'jQ Which possesses significant and singular properties in a 0 v C Cspecialized field of use. X It has been found that ferrocene hassignificant vola- G I C tility and because of this it has found favor asa burning C :OCHzOHzOOHzCHaCH: rate accelerator of solid propellantrocket fuels. However, i I the total dispersibility of ferrocene in thepropellant matrix is typically less than desirable. Modifications offerrocene H5 H4 by afiixing substituent groups on a cyclopentadienylradical thereof, e.g., acyloxy, keto and simple mono-ether, achieve onlymoderate improvements in the oompounds H -H- dispersibility in thepropellant matrix. c g 0 C This invention relates to ferrocenederivatives which possess substantially improved dispersibility in asolid pro- 0 pellant matrix and are excellent burning-rate accelerators.gmogmcmoomcmcmcm The ferrocene derivatives of this invention arecharacterized as a methylcycyopentadienyl cyclopentadienyl iron compoundhaving an aliphatic polyether radical bonded H4 H5 by an oxygen tocarbon bond to the methyl group. The aliphatic polyether radical may betermed an alkoxy- GT alkoxy or cycloalkoxyalkoxy group and analkoxypoly- I Be alkyleneoxy or cycloalkoxypolyalkyleneoxy group at- Ctached to the methyl group. These compounds may be characterized by theformula: 0 C

CHzOCHzCHz O CHzCHCHzCHgCHz OH: (I) H4 H5 49 OHrCHa.

C- }O 0---0 v i t n (i o o o 0 1 OG X H -FG-H ,-H-H,

O O CH1[O omcHmcmmoRl R C C 50 omoonzomcmoomon zcmom wherein at leastone of the Rs is hydrogen and not more than one of the Rs is an alkylgroup, typically of from 1 to 18 carbon atoms, and preferably of from 1to 8 car- H4 H, bon atoms; R is an alkyl group of from 1 to 18 carbonatoms and preferably from 1 to 12 carbon atoms, or a H cycloalkyl groupof from 4 to 8 carbon atoms preferably of from 5 to 8 carbon atoms; n isan integer of from 0 to C 0 C aobut 2; and m is an integer of from about1 to 6. Specific illustrations of aliphatic polyetheric substitutedferrocene encompassed within the above formula, include, 931001110320320310 CHZCHB as examples, l 7

a H5 H4 H6 (l u at n C Q X 0 0 0 0 0 o X c ioomcno omomomomCHzOCHzCHzOCH:

044; 04-0 :1 'l l' l C C C CH2OCHCH2OCH2CH3 H4 H5 C C (1+0 1" it ir ll CC C C C C CH QCEHCHOCHQ CH (5H2 l l l l C4) CHzCHzO CHzCHgO CH3 H4 C44ii ii CHQO CH CH O CHzCHaO CHzCHzCHzCHa I Ha C l c C l C o o '0,ocH'zoHocHmHocmcHa' Y CH3 cm 1 1 044 C-i-C ll li it ll 0 c o c C :0CHzCHaO CHzCHzO CHzCHaO CHgCHgO CHaCHa 1 CHQO CHzCHzO CHzCHqCHaCHnC CHzCCHzHgCHgCHzCHz CHzO CH2CHO CHzCHzCHzCHzCHgCHzCHzCHzCHnCHGCHzCHzCHzCHzCHzCHzCHzCHs H, H: Hg

0 0 o-o-o omocmomoomomoo CH1 and the like. Many other specific compoundsencompassed by Formula I are readily apparent and are included as partof this invention.

The above ferrocenyl compounds are advantageously obtained by thereaction of an alkali metal (e. g., Na, K, or Li) alcoholate of an etheralcohol, such as those of the formula mo omoHmcmmo R1 wherein R, R m andn are as described previously, with the methiodide or ethobromide of(dimethylarninomethyl)ferrocene, i.e.,

The iodine and bromide are described by Nesmeyanov et al., Iz-vestiyaAkademii Nauk SSSR, Otdelenie Khimicheskikh Nauk No. 3, pages 554-555(March 1960).

Specific aliphatic ether alcohols encompassed by Formula II include,e.g., the mono-methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl,n-pentyl, n-hexyl, 2-ethylhcxyl, n-octyl, n-nonyl, n-undecyl,n-octadecyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc.,ethers of ethylene glycol, di-, tri-, tetra-, penta-, heXa-ethyleneglycol, 1,2- and 1,3propylene glycol, 1,2-, 1,3- and 1,4-butyleneglycol, di, t1'i-, tetra-, penta-, hexa-1,2-, 1,3-, and 1,4-butyleneglycol,

1,2-, 1,3-, 1,4-penty1ene glycol, 1,2-, 1,3-, 1,4-hexylene glycol1,2-dodecylene glycol, 1,2-octadecylene glycol, 1,4- docosylene glycol,and the like.

The reaction may be elfected by simple admixture of the reactants at atemperature sufiicient to evolve amine from the reaction mixture.Typically the temperature of reaction is above 25 C., usually at least50 C., up to 200 C. Preferably, the reaction temperature is betweenabout 70 C. and 125 C. The alkali metal alcoholate of the ether alcoholis typically provided in at least a stoichiometric amount, i.e., atleast one mole of the alcoholate per mole of the methiodide orethobromide of (dimethylaminomethyl)ferrocene. In some instances, it maybe desirable to employ an amount of alcohol, as alcoholate, up to twicethe stoichiometric requirements.

The desired ferrocenyl product may be separated by dissolution of thereaction product mixture in an inert solvent, such as benzene, followedby Water and/or dilute acid washing. Upon drying, the desired productmay be obtained by conventional distillation.

The following examples are supplied in order to more specificallyexplain the invention and are not intended to be construed aslimitations on this invention.

Example I A solution of 4.5 grams of sodium in 250 milliliters ofmonobutyl ether of diethylene glycol is placed in a reaction flaskequipped with a stirrer thermometer and reflux condenser. 72 grams ofmethiodide of (dimethylaminomethyDferrocene (also calledferrocenylmethyltrimethylammonium iodide) is added to the flask and theresulting mixture is heated. At 100 C. trimethylamine is noted to beevolved. The temperature of the mixture is held at 100 to 110 C. for twohours. During this time the ferrocene salt is dissolved to give a deepred solution. The solution is cooled, diluted with 300 milliliters ofbenzene, and washed once with Water, once with dilute hydrochloric acidand twice with water. After drying over anhydrous potassium carbonate,the product is distilled. There is obtained 47 grams of the butyl etherof ferrocenylmethyloxyethyloxyethanol distilling 01f at 120 C. at 5microns pressure.

Example II Operating according to the procedure cited in Example I, themethiodide of (dimethylaminomethyl)ferrocene is reacted with theanhydrous sodium salt of the monoethyl ether of diethylene glycol toprovide good yields of the ethyl ether offerrocenylrnethyloxyethyloxyethanol.

Example 111 Operating according to the procedure cited in Example I, themethiodide of (dimethylaminomethyl)ferrocene is reacted with theanhydrous sodium salt of the monoethyl ether of ethylene glycol toprovide good yields of the ethyl ether of ferrocenylmethyloxyethanol.

Though the above relates to a plurality of specific details, such arenot intended to be considered as limitations on this invention unlessthey appear in the claims.

I claim:

1. Methylcyclopentadienyl cyclopentadienyl iron compound having aradical bonded to the methyl group from the class consisting ofalkoxyalkoxy, cycloalkoxyalkoxy, alkoxypolyalkyleneoxy andcycloalkoxypolyalkyleneoxy.

2. A ferrocene compound having the formula:

wherein at least one of the Rs is hydrogen and not more than one of theRs is an alkyl group; R is a member from the groups consisting of alkyland cycloalkyl; n is an integer of from 0 to about 2; and m is aninteger of from about 1 to 6.

3. The monobutyl ether of ferrocenylmethyloxyethyloxyethanol.

4. The monoethyl ether of ferrocenylmethyloxyethyloxyethanol.

5. The monoethyl ether of ferrocenylmethyloxyethanol.

6. A process for making methylcyclopentadienyl cyclopentadienyl ironcompound having an acyclic aliphatic polyether radical from the classconsisting of alkoxyalkoxy, cycloalkoxyalkoxy, alkoxypolyalkyleneoxy andcycloalkoxypolyalkyleneoxy, bonded by an oxygen to carbon bond to themethyl group which comprises reacting an alkali metal alcoholate of anether alcohol corresponding to said aliphatic polyether radical with acompound from the class consisting of the methiodide and ethobromide of(dimethylarninomethyl)ferrocene.

vol. 22, No. 4, May

UNITED STATES PATENT ()FEICE CERTIFICATE OF CORRECTION Patent No 3 ,322,804 May 30 1967 Roy L. Pruett It is hereby certified that error appearsin the above numbered patent requiring correction and that the saidLetters Patent should read as corrected below.

Column 3, lines 67 to 75, the formula should appear as shown belowinstead of as in the patent:

C C C C H OCH CH OCH CH OCH CH CH CH CH CH CH CH3 Signed and sealed this9th day of January 1968 Attest:

Edward M. Fletcher, J1. EDWARD J. BRENNER Attesting Officer Commissionerof Patents

1. METHYLCYCLOPENTADIENYL CYCLOPENTADIENYL IRON COMPOUND HAVING ARADICAL BONDED TO THE METHYL GROUP FROM THE CLASS CONSISTING OFALKOXYALKOXY, CYCLOALKOXYALKOXY, ALKOXYPOLYALKYLENEOXY ANDCYCLOALKOXYPOLYALKYLENEOXY.